CN108314019A - A kind of preparation method of the uniform large-area high-quality graphene film of the number of plies - Google Patents
A kind of preparation method of the uniform large-area high-quality graphene film of the number of plies Download PDFInfo
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Abstract
The invention discloses a kind of using 2 naphthols as solid-state carbon source, and 1 octyl phosphonic acid directly prepares graphene film on silicon (Si) substrate as auxiliary carbon source by chemical vapor deposition (CVD) method.Compared with traditional metal surface catalysis prepares the method for graphene film, the advantage of the invention is the direct preparation of film, eliminates the transfering process of film, avoids the phenomenon that graphene film causes compromised quality due to transfer.The present invention utilizes CVD method to combine two kinds of solid-state carbon source for growth graphene films for the first time, improves the quality of forming film of graphene film, coverage rate and large area.This method is simple for process, convenient for control, is suitably applied routine experimentation and production, also, graphene film is employed for various fields as current most burning hot one of two-dimensional semiconductor material.Therefore, the present invention has higher application value and meaning to the preparation and production of graphene film.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of uniform large-area high-quality graphene of the number of plies is thin
The preparation method of film.
Background technology
Graphene is the two-dimentional carbon nanomaterial being made of one layer of carbon atom, the monoatomic layer phase of atomic arrangement and graphite
Together, it is single layer two dimensional crystal that carbon atom is arranged to make up with sp2 hybridized orbits by honeycomb lattice.Graphene is most surprisingly
Its very special electrical properties is different with other most two-dimensional materials, it is a zero gap semiconductor, which takes
Certainly in its special band structure.Graphene has very high charge mobility, and experiment, which shows graphene at room temperature, to be had greatly
In the carrier mobility of 15000cm2V-1s-1, which is not affected by temperature and reaches as high as substantially
20000cm2V-1s-1, relative resistivities are 10-6 Ω cm, and graphene also has in surprise optical in addition to this
Matter (there are about 3.2% absorptions to visible light for single-layer graphene), (in theory, the thermal conductivity of graphene is reachable for thermal conductivity property
1000Wm-1K-1), mechanical property (Young's modulus of graphene is up to 1.0TPa, and fracture strength is up to 42Nm-1,
It is 200 times of steel) etc..So graphene is likely to become next-generation base electronic component and has a good application prospect, it can
It applies in fields such as spin electric device, laser switch, photonic crystal, thermoelectric devices.Currently, the side of being synthetically prepared of graphene
There are many method, can be divided into physical method and chemical method substantially, such as：Mechanical stripping, epitaxial growth, chemical vapor deposition (CVD),
Chemical stripping, chemical synthesis etc..Wherein CVD method is of great significance to application of the graphene in terms of microelectronics, is current public affairs
The most promising graphene preparation method recognized.
Chemical vapor deposition (CVD) method is a kind of by heating carbon-source gas (such as acetylene, methane), liquid (benzene etc.) very
To solid (macromolecule etc.) material to certain temperature, carbon atom can give birth on some surfaces metal (such as monocrystalline Cu, polycrystalline Ni)
At the method for graphene film.This method has great relationship with the solubility of carbon atom in a metal.Currently, using CVD method
It is Cu and Ni to grow the most common metal of graphene.Researcher has found that carbon atom possesses good dissolubility in Ni substrates,
Graphene can be described as in the growth mechanism of Ni substrate surfaces during CVD：Hydrocarbon is in metal surface point under high temperature
Carbon atom is solved and releases, carbon atom forms carbide solid solution with metallic nickel, and then is diffused into Ni substrate interiors.Carbon after cooling
Atom is precipitated due to the solubility supersaturation in Ni substrates from Ni metal insides, and assembles to form graphite in Ni substrate surfaces
Alkene, this growth mechanism are called solution modeling mechanism.Compared with the mechanism of Ni substrate catalytic growth graphenes, graphite on Cu substrates
The growth of alkene includes the dispersion and diffusion into the surface of hydrocarbon closer to surface catalysis process, and detailed process is hydrocarbonization
It closes object to adsorb and be desorbed in Cu substrate surfaces, after hydrocarbon resolves into carbon atom, carbon atom forms more in Cu substrate surfaces
A graphene nuclearing centre, and then other carbon atoms are constantly diffused into around graphene nuclearing centre is linked to be stone by chemical bond
Black alkene film.The country has had a large amount of worker to be engaged in graphene film and has prepared and achieve certain achievement at present.
It is required for metal as catalyst in conclusion the current generation prepares graphene film, so being substantially in Cu
Or Ni Grown graphenes, but many applications of current graphene, such as in application prepared by graphene device, need
The graphene film of Cu or Ni substrate surfaces is transferred in target substrate.The transfer techniques of graphene develop to today,
Through there is more than 30 kinds of transfer method.These methods are had nothing in common with each other, and respectively have length.However, transfer process is easy the quality to graphene
Generate irreversible damage.Therefore it is directly to have very much by the method that graphene film is prepared into target substrate surface to find a kind of
Meaning.
Some researchers have prepared graphene film in the way of thermal evaporation in Si substrate surfaces at present, however,
The quality and uniformity for the graphene film prepared using the technique are poor.In the present invention, magnetron sputtering method and change are utilized
It learns vapour deposition process to be combined, by the methods of Optimizing Process Parameters, improvement carbon source, finding one kind can be directly in target substrate
Upper preparation mass is higher, the preferable graphene film of uniformity.
Invention content
For the defect and deficiency of existing technology of preparing, the present invention provides a kind of directly preparation number of plies on a si substrate is equal
The new method of even high-quality graphene film, preparation method find efficient solid-state carbon source from two basic points, first,
Improve the defect that graphene film is likely to occur in growth course；Second, by modified technique flow, further increase graphite
The quality of alkene film.
To solve the above problems, the technical solution that the present invention takes is：
A kind of preparation method of the uniform large-area high-quality graphene film of the number of plies, this method be using beta naphthal as
Solid-state carbon source, is combined that graphene is directly prepared on required substrate is thin by magnetron sputtering technique and chemical vapour deposition technique
The method of film；Specifically comprise the following steps：
The concentrated sulfuric acid for being 98% with purity and 30% hydrogen peroxide are according to 7:3 proportional arrangement Piranha solution, silicon is served as a contrast
Bottom is immersed in Piranha solution and cleans, then is cleaned by ultrasonic respectively to silicon substrate with acetone, absolute ethyl alcohol, deionized water；
Solid-state carbon source beta naphthal and 1- octyl phosphonic acids are dissolved in chloroform, by magnetic agitation so that carbon source is completely dissolved
In chloroformic solution；
Using sol evenning machine the solid-state carbon source in chloroform is had been dissolved in clean Si substrate surface spin coatings；
Substrate surface after spin coating carbon source prepares Copper thin film using rf magnetron sputtering technique；
Substrate after sputtering is put into CVD and grows graphene.
Further, further include sputtering the substrate after Cu films in spin coating carbon source and can be obtained growth uniformity in CVD
Well, the high-quality graphene film of large area；
Wherein, the specification of Si substrates is 10*10*1mm；
In the spin coating carbon source stage, solid-state carbon source is made of 2- naphthalenes sweet smell and auxiliary carbon source 1- octyl phosphonic acids respectively；By spin coating
Si substrates after solid-state carbon source are put into rf magnetron sputtering system,
Cu atoms are sputtered in the substrate surface, the effect of copper atom is that solid-state carbon source is catalytically decomposed at high temperature；
In the graphene growth stage, it is passed through argon gas, hydrogen gas mixture, wherein argon gas is protective gas, and hydrogen is as also
Raw-gas.
Further, the solid-state carbon source is the mixture of 2- naphthalenes sweet smell and 1- octyl phosphonic acids, and it is 9 to match:1.
Further, in the chloroform carbon source a concentration of 0.4%.
Further, the spin coating parameters are rotating speed 3000r/s under 20 DEG C of environment；In spin coating process, carbon source dosage is
2~4 drops are often divided into 2s between drop carbon source solution min.
Further, the radio-frequency power of sputtering Cu films is 150W, sputtering time 120min.
Further, the Ar flows of Si Growns graphene are 200sccm in CVD；
Further, the H2 flows of Si Growns graphene are 100sccm in CVD；
Further, the inside cavity pressure of Si Growns graphene is 0.5Toor in CVD；
Further, the temperature of growth graphene film is 400~600 DEG C on a si substrate during CVD；
Further, the time of growth graphene film is 60~120min on a si substrate during CVD；
Further, the rate of temperature fall of growth graphene film is 25 DEG C/s on a si substrate during CVD.
The present invention has the advantages that：
1) successful omission transfer step, directly prepares graphene film in target substrate.
2) new trial has been carried out in the selection of carbon source material.First, it is primary carbon source to select beta naphthal, is contained in structure
There is phenyl ring, and contain hydroxyl, hydroxyl is heated easy fracture, is conducive to the growth of graphene.Select 1- octyl phosphonic acids as auxiliary again
Carbon source, the heated vacancy-like defects for being easily decomposed into small molecule carbon source, being conducive in the graphene that repairing is grown of 1- octyl phosphonic acids.
3) copper atom is sputtered as catalyst in the substrate surface of spin coating carbon source using magnetron sputtering technique.Magnetron sputtering
Technological process facilitate control, be conducive to the optimization of preparation flow.
4) this technique compares existing technique, has very big breakthrough, is on the one hand directly to grow graphite in target substrate
Transfer step is omitted in alkene, is conducive to application of the graphene film in terms of device；On the other hand, prepared by graphene film
Technological parameter in journey accurately controls, and graphene film quality is high, and number of plies uniformity is good, suitable for mass production, is conducive to stone
Application of the black alkene film in terms of device.
5) source material safety and environmental protection of the present invention not will produce toxic or environmentally harmful substance.
Description of the drawings
Fig. 1 is the substrate pictorial diagram in embodiment after sputtering Cu films in the present invention；
Fig. 2 is the pictorial diagram for the graphene sample that CVD annealing is prepared after the completion in embodiment in the present invention；
Fig. 3 is the XRD spectrum for sputtering Cu films in the present invention in embodiment；
Fig. 4 is the Raman collection of illustrative plates of the graphene sample prepared in embodiment in the present invention；
Fig. 5 is the Raman collection of illustrative plates of the graphene sample prepared in embodiment in the present invention；
Fig. 6 is the TEM of the graphene sample prepared in embodiment in the present invention and chooses electron diffraction diagram；
Fig. 7 is the Raman collection of illustrative plates of the Cu substrate graphene samples prepared in comparative example 1 in the present invention；
Fig. 8 is the Raman collection of illustrative plates of graphene sample after being transferred to Si substrates in the present invention in comparative example 1；
Fig. 9 is the Raman collection of illustrative plates of the graphene sample prepared in comparative example 2 in the present invention.
Specific implementation mode
Below in conjunction with attached drawing and specific embodiment, the present invention will be described in detail, herein illustrative examples of the invention
And explanation is used for explaining the present invention, but it is not as a limitation of the invention.
The present invention is to rapidly develop using magnetron sputtering technique (Magnetron Sputtering) the 1970s
A kind of coating technique come, is the method for comparative maturity in coating technique.The essence of sputtering technology is a kind of physical vapour deposition (PVD)
Method, Ar gas, which is ionized, under high voltages is decomposed into Ar2+ and free electron, does cycle movement to target material surface, makes target
Atom or molecule are shelled out, and the technology being deposited on substrate surface used.And in original when magnetron sputtering
A magnetic field is added between the two poles of the earth of this electric field so that electronics is not only influenced the shadow also by magnetic field Lorentz force by electric field
It ringing, and changes the movement locus of electronics so that electronics and Ar2+ collision probabilities increase, and improve the degree of ionization of Ar qi leel,
So as to improve sputtering, deposition efficiency.
Chemical vapor deposition (CVD) refers to the gas phase reaction under high temperature, for example, metal halide, organic metal, hydrocarbon
The thermal decomposition of compound etc., hydrogen reduction or make its mixed gas occur at high temperature chemical reaction with precipitating metal, oxide,
The method of the inorganic material such as carbide.This technology is initially to be developed as the means of coating, but be not only applied to heat-resisting
The coating of substance, and applied to the refined of high purity metal, powder synthesis, semiconductive thin film etc., be one and have much feature
Technical field.It is technically characterized in that：High-melting-point substances can synthesize at low temperature；Be precipitated substance form monocrystalline, polycrystalline,
Whisker, powder, film etc. are a variety of；Can not only carry out coating on substrate, and can in powder surface coating, etc..Especially
Be that can synthesize high-melting-point substances at low temperature, contribution be made that at energy saving aspect, be as a kind of new technology it is coming,
Equally, graphene film field is being prepared, CVD technology is also acknowledged as preparing large-area high-quality graphene film most suitable
Method.
Embodiment 1：
The present embodiment provides one kind by magnetron sputtering and chemical vapour deposition technique, omits transfer step in Si substrates
Surface directly grows high-quality graphene film, includes the following steps：
Step 1：Piranha solution is prepared first, in order to thoroughly remove the organic impurities of substrate surface, and increases substrate
The hydrophily on surface, we handle substrate with Piranha solution first, and Piranha solution (piranha solution) is called food
Mermaid etching liquid is the mixture of dense H2SO4 and 30%H2O2, volume ratio 7:3.It is in process for preparation, H2O2 is slow
It pours into dense H2SO4, and is stirred continuously, prevent bumping.The Piranha solution configured is down to room temperature, for use.
Step 2：It is 1 to place the substrate into volume ratio:Surpass respectively in 1 acetone and carbon tetrachloride mixed liquor and absolute ethyl alcohol
Sound cleans 30min, tentatively to remove surface impurity, then places the substrate into Piranha solution, and heating water bath impregnates 30 to 80 DEG C
Minute.Taking-up is cleaned several times repeatedly with deionized water, and nitrogen gun is used in combination to dry up, for use.
Step 3：It weighs the beta naphthal and 0.004g 1- octyl phosphonic acids of 0.036g respectively with balance, and mixes and be put into 10ml
It in chloroform, is placed on magnetic stirrer and stirs, make its all fully dissolving.Setting spin coating parameter in next step, control spin coating temperature are permanent
It is fixed, spin coating the speed 3000r/min, spin coating time 60s of sol evenning machine are set.Substrate for use in previous step is placed on glue evenning table
On, sol evenning machine is directly opened, then beta naphthal, the 1- octyl phosphonic acid mixed solutions fully dissolved is drawn with dropper, waits for sol evenning machine
After running 10s, start at the uniform velocity to drip 4 drop of carbon source solution on substrate as time interval using 2s.After waiting for spin coating, then the 10s that dallies
Until chloroform volatilizees completely, finally sol evenning machine is closed, substrate is taken out, it is for use to be put into quartz boat.
Step 4：Substrate after spin coating is put into the sample room of magnetic control sputtering system, in room temperature, 0.5Pa pressure,
Under the conditions of Ar gas velocity 20sccm, sputtering power 150W after pre-sputtering 30min, 120min is sputtered.
Step 5：The substrate sputtered is put into tube-type atmosphere furnace (CVD), using Ar gas Cleaning pipes, with thoroughly clear
Except the O2 gas in pipeline, then vacuumize.Ar throughputs are adjusted to 200sccm again, H2 flows are 100sccm, and electric furnace is arranged
Temperature in pipe is risen to 600 DEG C by startup program with the heating rate of 8 DEG C/min, after temperature stabilization, keeps 120min.Terminate
Afterwards, H2 air valves are closed rapidly, and mobile electric furnace opens wind turbine, the short annealing cooling under Ar gas atmosphere.
Step 6：A certain amount of FeCl3 is dissolved into deionized water, the sample that annealing finishes is put into FeCl3 solution
In, impregnate 12 hours or more, to thoroughly remove the Cu films on substrate, then sample is taken out, is dried up with nitrogen gun, is put into dustless
It is preserved in paper.
Fig. 1 is the substrate picture after having sputtered, and purple part is unsintered tape shield portions in figure.Fig. 2 finishes for annealing, and
By the picture after the Cu membrane removals of sputtering, unsintered tape shield portions do not have graphene generation before sputtering can be clearly seen.Fig. 3 is
Sputter the XRD diagram picture of Cu films, it can be seen that other material property peaks are not present in the Cu film surfaces after sputtering.Fig. 4~Fig. 5 is in Si
It is prepared using CVD method on substrate and randomly selects the Raman light that test obtains in substrate surface using Raman spectroscopy after graphene film
Spectrum, Raman spectrum are the reaction graphene film number of plies and the most effective characterization method of crystalline quality.For grapheme material,
Its characteristic peak is located in figure at 1350cm-1,1580cm-1 and 2750cm-1 of X-direction, and wherein the peaks D are used for indicating stone
The defect and randomness of black alkene film, so the height at the peaks D determines the quality of graphene, as can be seen from the figure this technique system
Raman spectrum for the graphene film gone out does not have the apparent peaks D, illustrates the graphite that high quality is easy to get using this set technique
Alkene film, meanwhile, the number of plies of graphene film at this is estimated that using the ratio of the peaks 2D and the peaks G peak intensity, it can be with from figure
Find out that the ratio at the peaks 2D and the peaks G is in a certain range in four obtained Raman spectrums of the test point randomly selected, performance
The uniformity of the film number of plies is gone out.Fig. 6 be prepare graphene sample TEM and choose electron diffraction diagram, by TEM it can be seen that
Prepared graphene sample is more uniform.Electron diffraction diagram is chosen, is typical graphene diffraction image, it can be deduced that made
Possess good crystallinity for the graphene sample gone out.
Comparative example 1：
This comparative example provides one kind and directly growing graphene in Cu substrate surfaces, and wet method transfer is recycled to shift graphene
Onto Si substrate, graphene film is prepared using the identical spin coating with embodiment and CVD technological parameters, is included the following steps,
Step 1：It is 1 to place the substrate into volume ratio:1 acetone and carbon tetrachloride mixed liquor, absolute ethyl alcohol, deionized water
It is middle to be cleaned by ultrasonic 30min respectively, it is used in combination nitrogen gun to dry up, for use.
Step 2：It weighs the beta naphthal and 0.004g 1- octyl phosphonic acids of 0.036g respectively with balance, and mixes and be put into 10ml
It in chloroform, is placed on magnetic stirrer and stirs, make its all fully dissolving.Setting spin coating parameter is the same with last chapter in next step, control
Spin coating temperature is constant, and spin coating the speed 3000r/min, spin coating time 60s of sol evenning machine is arranged.Substrate for use in previous step is put
On glue evenning table, sol evenning machine is directly opened, then draws beta naphthal, the 1- octyl phosphonic acid mixed solutions fully dissolved with dropper,
After sol evenning machine runs 10s, start at the uniform velocity to drip 4 drop of carbon source solution on substrate as time interval using 2s.After waiting for spin coating, then
Idle running 10s volatilizees completely up to chloroform, finally closes sol evenning machine, takes out substrate, it is for use to be put into quartz boat.
Step 3：The good substrate of spin coating is put into tube-type atmosphere furnace (CVD), using Ar gas Cleaning pipes, with thoroughly clear
Except the O2 gas in pipeline, then vacuumize.Ar throughputs are adjusted to 200sccm again, H2 flows are 100sccm, and electric furnace is arranged
Temperature in pipe is risen to 600 DEG C by startup program with the heating rate of 8 DEG C/min, after temperature stabilization, keeps 60min.Terminate
Afterwards, H2 air valves are closed rapidly, and mobile electric furnace opens wind turbine, the short annealing cooling under Ar gas atmosphere.
Step 4：PMMA is put into glacial acetic acid, being placed on magnetic stirrer makes it fully dissolve；There is graphene in growth
Cu substrates on spin coating PMMA solution, and dry for use；
Step 5：Sample after spin coating is put into FeCl3 solution, is taken out after Cu substrates are completely dissolved；
Step 6：By the graphene of taking-up/PMMA films, according to PMMA upper, structure of the graphene under is attached to Si linings
On bottom；
Step 7：Si substrates are put into acetone and are impregnated, takes out, dries after PMMA is completely dissolved, be put into dust-free paper
It is spare
Fig. 8 is the Raman spectrogram in Cu Grown graphene samples using solid-state carbon source.Fig. 9 is to utilize PMMA mistakes
Graphene on Cu substrates is transferred to the Raman spectrogram after Si substrates by the wet method transfer method crossed.It can be significantly from figure
The D peak-to-peak values gone out in Fig. 9 have a prodigious raising compared to Fig. 8, illustrate that the defect concentration of the graphene film after transfer increases
Add.Fig. 9 is Si substrate graphenes with Fig. 4~6 in embodiment, but utilizes the stone of the invention directly grown on a si substrate
D peak-to-peak values in the Raman spectrogram (Fig. 4~6) of black alkene sample will be much smaller than the graphene (Fig. 9) after transfer, illustrate to utilize this
Invention, can effectively promote the quality of forming film of Si substrate graphene films, make Si substrates graphene evenly, defect concentration is more
It is low.
Comparative example 2：
It is only solid-state carbon source using beta naphthal that this comparative example, which provides a kind of, in the case of not adding auxiliary carbon source, is served as a contrast in Si
Bottom surface grows graphene, and graphene film is prepared using the identical spin coating with embodiment, sputtering, CVD technological parameters, including
Following steps：
Step 1：It is identical to the cleaning method of substrate with embodiment；
Step 2：It is identical as embodiment；
Step 3：Weigh with scale the beta naphthal of 0.04g, and dissolves in 10ml chloroforms, is placed on magnetic stirrer and stirs,
Make its all fully dissolving.Remaining steps are identical as embodiment；
Step 4：It is identical as embodiment；
Step 5：It is identical as embodiment；
Step 6：It is identical as embodiment；
Fig. 9 is to utilize single carbon source on a si substrate, is prepared by CVD method and is being served as a contrast using Raman spectroscopy after graphene film
Bottom surface randomly selects the Raman spectrum that test obtains, and compared with Fig. 4, Fig. 5, the D peak-to-peak values for representing defect are higher, and surface is single
The defect concentration for the graphene film that one carbon source is prepared in target substrate is higher.Therefore deduce that the present invention utilizes 2- naphthalenes
The quality for the graphene film that phenol and 1- octyl phosphonic acid mixed carbon sources are prepared has promotion largely.
The technical solution disclosed in the embodiment of the present invention is described in detail above, specific implementation used herein
Example is expounded the principle and embodiment of the embodiment of the present invention, and the explanation of above example is only applicable to help to understand
The principle of the embodiment of the present invention；Meanwhile for those of ordinary skill in the art, embodiment, is being embodied according to the present invention
There will be changes in mode and application range, in conclusion the content of the present specification should not be construed as the limit to the present invention
System.
Claims (7)
1. a kind of preparation method of the uniform large-area high-quality graphene film of the number of plies, this method is using beta naphthal as solid
State carbon source is combined by magnetron sputtering technique and chemical vapour deposition technique and directly prepares graphene film on required substrate
Method；Specifically comprise the following steps：
The concentrated sulfuric acid for being 98% with purity and 30% hydrogen peroxide are according to 7:3 proportional arrangement Piranha solution, silicon substrate is soaked
Bubble cleans in Piranha solution, then is cleaned by ultrasonic respectively to silicon substrate with acetone, absolute ethyl alcohol, deionized water；
Solid-state carbon source beta naphthal and 1- octyl phosphonic acids are dissolved in chloroform, by magnetic agitation so that carbon source is dissolved completely in chlorine
In imitative solution；
Using sol evenning machine the solid-state carbon source in chloroform is had been dissolved in clean Si substrate surface spin coatings；
Substrate surface after spin coating carbon source prepares Copper thin film using rf magnetron sputtering technique；
Substrate after sputtering is put into CVD and grows graphene.
2. preparation method according to claim 1, which is characterized in that further include in spin coating carbon source, after sputtering Cu films
Substrate can be obtained in CVD growth have good uniformity, the high-quality graphene film of large area；
Wherein, the specification of Si substrates is 10*10*1mm；
In the spin coating carbon source stage, solid-state carbon source is made of 2- naphthalenes sweet smell and auxiliary carbon source 1- octyl phosphonic acids respectively；By spin coating solid-state
Si substrates after carbon source are put into rf magnetron sputtering system,
Cu atoms are sputtered in the substrate surface, the effect of copper atom is that solid-state carbon source is catalytically decomposed at high temperature；
In the graphene growth stage, it is passed through argon gas, hydrogen gas mixture, wherein argon gas is protective gas, and hydrogen is as also Primordial Qi
Body.
3. preparation method according to claim 2, which is characterized in that the solid-state carbon source is 2- naphthalenes sweet smell and 1- octyl phosphonic acids
Mixture, it is 9 to match:1.
4. preparation method according to claim 1, which is characterized in that a concentration of the 0.4% of carbon source in the chloroform.
5. preparation method according to claim 1 or 2, which is characterized in that the spin coating parameters are rotating speed under 20 DEG C of environment
For 3000r/s；In spin coating process, carbon source dosage is 2~4 drops, is often divided into 2s between drop carbon source solution min.
6. preparation method according to claim 1 or 2, which is characterized in that the radio-frequency power of sputtering Cu films is 150W, is splashed
It is 120min to penetrate the time.
7. preparation method according to claim 1 or 2, which is characterized in that
The Ar flows of Si Growns graphene are 200sccm in CVD；
The H2 flows of Si Growns graphene are 100sccm in CVD；
The inside cavity pressure of Si Growns graphene is 0.5Toor in CVD；
The temperature of growth graphene film is 400~600 DEG C on a si substrate during CVD；
The time of growth graphene film is 60~120min on a si substrate during CVD；
The rate of temperature fall of growth graphene film is 25 DEG C/s on a si substrate during CVD.
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| CN109516442A (en) * | 2018-12-26 | 2019-03-26 | 科洋环境工程（上海）有限公司 | Convert sulfur-containing smoke gas to the process system and process of sulfuric acid |
| CN110040725A (en) * | 2019-03-13 | 2019-07-23 | 中国科学院金属研究所 | A kind of method of the uniform number of plies graphene film of quick preparation high quality |
| CN115323347A (en) * | 2022-07-01 | 2022-11-11 | 中国石油大学(华东) | Iron-based substrate and method for producing graphene by using same |
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| CN109052377B (en) * | 2018-10-25 | 2020-05-22 | 济南大学 | Preparation method of large-area graphene |
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